JP6419342B2 - Pattern forming method and electronic device manufacturing method - Google Patents

Description

  The present invention relates to a developer containing an organic solvent that is suitably used in ultra microlithography processes such as manufacturing of large scale integrated circuits (VLSI) and high-capacity microchips and other photofabrication processes. The present invention relates to a pattern forming method, an electronic device manufacturing method, and a resist composition. More specifically, a pattern forming method using a developer containing an organic solvent, which can be suitably used for microfabrication of a semiconductor element using an electron beam or EUV light (Extreme Ultra Violet, extreme ultraviolet light, wavelength: around 13 nm), The present invention relates to an electronic device manufacturing method and a resist composition.

  Conventionally, in a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) and an LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this trend, the trend of shortening the exposure wavelength from g-line to i-line and further to excimer laser light has been observed. At present, the development of lithography using electron beam, X-ray or EUV light is progressing. Yes.

By the way, in the actinic ray-sensitive or radiation-sensitive resin composition, a pattern is generally formed by using a resin that is hardly soluble or insoluble in an alkali developer and solubilizing an exposed portion in the alkali developer by exposure. There are a “positive type” and a “negative type” in which a resin is soluble in an alkali developer and a pattern is formed by making an exposed portion insoluble or insoluble in an alkali developer by exposure.
As an actinic ray-sensitive or radiation-sensitive resin composition suitable for such a lithographic process, a chemically amplified positive resist composition mainly utilizing an acid-catalyzed reaction has been studied from the viewpoint of high sensitivity. A chemically amplified positive resist composition comprising a resin that is insoluble or hardly soluble in an alkali developer and is soluble in an alkali developer by the action of an acid, and an acid generator is effectively used. (For example, Patent Documents 1 to 3).

On the other hand, in the manufacture of semiconductor elements and the like, there is a demand for forming patterns having various shapes such as lines, trenches and holes. In order to meet the demand for pattern formation having various shapes, not only positive type but also negative type actinic ray-sensitive or radiation-sensitive resin compositions have been developed.
In the formation of ultrafine patterns, a method of developing an acid-decomposable resin with a developer other than an alkali developer has been proposed for improving the resolution and further improving the pattern shape (for example, patent documents). 4-6).

JP 2013-1000047 A Japanese Patent Application Laid-Open No. 2013-100472 JP 2013-1000047 A JP 2013-68675 A JP 2011-221513 A JP2015-31851A

  However, in the pattern forming method described above, a very fine pattern (for example, a line-and-space pattern with a line width of 50 nm or less, a dot pattern with a diameter of 50 nm or less) is caused by swelling due to penetration of a developer containing an organic solvent into the pattern. At the time of formation, pattern collapse occurred, and sufficient resolving power was not obtained.

  In view of the above problems, an object of the present invention is to provide a pattern forming method, an electronic device manufacturing method, and a resist having high sensitivity and high resolving power when forming an extremely fine pattern (for example, a dot pattern having a diameter of 50 nm or less). It is to provide a composition.

As a result of intensive studies, the present inventors have used a resist composition in which a resin having a highly polar repeating unit, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a solvent are used, and includes an organic solvent. It has been found that the above object can be achieved by a method of forming a pattern by developing with a developer.
That is, the above problem can be solved by the following means.
<1>
(A) a resin represented by the following general formula (4), which contains a repeating unit having a ClogP value of 2.2 or less, and whose solubility in a developer containing an organic solvent is reduced by the action of an acid; and (B) activity A step (1) of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with light or radiation, and (C) a solvent;
Exposing the film with actinic rays or radiation (2), and
Developing the film exposed in the step (2) using a developer containing an organic solvent to form a negative pattern (3),
The pattern formation method whose content of the said organic solvent in the said developing solution is more than 50 mass% and 100 mass% or less with respect to the whole quantity of the said developing solution.

In general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
<2>
The pattern formation method as described in <1> in which the said resin (A) contains the repeating unit which has an acid-decomposable group.
<3>
The pattern formation method according to <1> or <2>, wherein the general formula (4) is represented by the following general formula (4a).

In general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4 . If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
<4>
R ₄ is represented by a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), or a following general formula (N2). The pattern formation method according to any one of <1> to <3>, which represents a group, a group represented by the following general formula (S1), or a group represented by the following general formula (S2).

In General Formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
In General Formula (N2), R _N3 represents a substituent, and R _N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
<5>
<1> to <4>, wherein R ₄ is a hydroxyl group, a hydroxymethyl group, a carboxyl group, a group represented by the following general formula (S1), or a group represented by the following general formula (S2) The pattern formation method of any one of Claims 1.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
<6>
It said ^{n 3} is an integer of 0 to 2, <1> - pattern forming method according to any one of <5>.
<7>
The pattern formation method according to any one of <1> to <6>, wherein the compound (B) is a sulfonium salt.
<8>
The compound (B), the volume of the generated acid is 130 Å ³ or more 2000 Å ³ or less, the pattern forming method according to <7>.
<9>
The pattern formation method according to any one of <1> to <8>, wherein the resin (A) further includes a repeating unit having a lactone group.
<10>
<1>-<9> The manufacturing method of an electronic device containing the pattern formation method of any one of <9>.
Although the present invention relates to the above <1> to <10>, other matters are also described in this specification for reference.

[1]
(A) a resin represented by the following general formula (1), which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is reduced by the action of an acid; and (B) activity A step (1) of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with light or radiation, and (C) a solvent;
A step (2) of exposing the film using actinic rays or radiation, and a step of developing the film exposed in the step (2) using a developer containing an organic solvent to form a negative pattern ( 3) A pattern forming method.

In general formula (1), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, or a carboxyl group, and L represents a single bond or a divalent group. Represents a linking group. R ₂ or R ₃ and L may combine with each other to form a ring, in which case either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Represent. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[2]
The pattern forming method according to [1], wherein the resin (A) includes a repeating unit having an acid-decomposable group.
[3]
The pattern formation method according to [1] or [2], wherein at least one of R _{4 in} the general formula (1) is a hydroxyl group.
[4]
The pattern formation method according to any one of [1] to [3], wherein the general formula (1) is represented by the following general formula (2).

In general formula (2), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, or a carboxyl group, and L represents a single bond or a divalent group. Represents a linking group. R ₂ or R ₃ and L may combine with each other to form a ring, in which case either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Represent. R ₄ represents a substituent, and n ² represents an integer of 0 to 4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[5]
The pattern formation method according to any one of [1] to [4], wherein the general formula (1) is represented by the following general formula (3).

In General Formula (3), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, and L represents a single bond or a divalent linking group. R ₄ represents a substituent. n ² represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[6]
The pattern formation method according to any one of [1] to [4], wherein the general formula (1) is represented by the following general formula (4).

In general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[7]
The pattern formation method according to [6], wherein the general formula (4) is represented by the following general formula (4a).

In general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[8]
R ₄ is represented by a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), or a following general formula (N2). The pattern formation method according to any one of [1] to [7], which represents a group, a group represented by the following general formula (S1), or a group represented by the following general formula (S2).

In General Formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
In General Formula (N2), R _N3 represents a substituent, and R _N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
[9]
The above R ₄ is a hydroxyl group, a hydroxymethyl group, a carboxyl group, a group represented by the above general formula (S1), or a group represented by the above general formula (S2), [1] to [8] The pattern formation method of any one of Claims 1.
[10]
The pattern forming method according to [4] or [5], wherein the n ² is 1 or 2.
[11]
Said ^{n 3} is an integer from 0 to 2, the pattern forming method according to [6] or [7].
[12]
The pattern forming method according to any one of [1] to [11], wherein the compound (B) is a sulfonium salt.
[13]
The compound (B), the volume of the generated acid is 130 Å ³ or more 2000 Å ³ or less, the pattern forming method according to [12].
[14]
The pattern forming method according to any one of [1] to [13], wherein the resin (A) further includes a repeating unit having a lactone group.
[15]
The manufacturing method of an electronic device containing the pattern formation method of any one of [1]-[14].
[16]
The resist composition containing resin which has a repeating unit represented by following General formula (4).

In general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[17]
The resist composition according to [16], wherein the general formula (4) is represented by the following general formula (4a).

In general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.
[18]
R ₄ is represented by a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), or a following general formula (N2). The resist composition according to [16] or [17], which represents a group, a group represented by the following general formula (S1), or a group represented by the following general formula (S2).

In General Formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
In General Formula (N2), R _N3 represents a substituent, and R _N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

  According to the present invention, when a very fine pattern (for example, a line-and-space pattern with a line width of 50 nm or less, a dot pattern with a diameter of 50 nm or less) is formed, a pattern forming method with high sensitivity and high resolving power, and a method for manufacturing an electronic device And a resist composition can be provided.

Below, an example of the form for implementing this invention is demonstrated.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, electron beams and the like. In the present invention, “light” means actinic rays or radiation. Unless otherwise specified, “exposure” in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, X-rays, extreme ultraviolet rays (EUV light), but also EB (electron beam). ) And drawing with a particle beam such as an ion beam are also included in the exposure.
In addition, in the description of group (atomic group) in this specification, the description which is not describing substitution or non-substitution includes what has a substituent in addition to what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "(meth) acrylic monomer" means at least one monomer having the structure of _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
In the present specification, the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method. GPC uses HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column, and THF (tetrahydrofuran) as an eluent. You can follow the same method.

[Pattern formation method]
First, the pattern forming method of the present invention will be described.
The pattern forming method of the present invention comprises:
(A) a resin represented by the following general formula (1), which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is reduced by the action of an acid; and (B) activity A step (1) of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with light or radiation, and (C) a solvent;
A step (2) of exposing the film using actinic rays or radiation, and a step of developing the film exposed in the step (2) using a developer containing an organic solvent to form a negative pattern ( 3) having a pattern forming method.

In general formula (1), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, or a carboxyl group, and L represents a single bond or a divalent group. Represents a linking group. R ₂ or R ₃ and L may combine with each other to form a ring, in which case either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Represent. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.

  The pattern forming method of the present invention has high sensitivity and high resolving power when forming an extremely fine pattern (for example, a dot pattern having a diameter of 50 nm or less). The reason is not clear, but is estimated as follows.

  The main factors that make it impossible to form an extremely fine pattern are pattern collapse and pattern collapse. These phenomena occur when the developer penetrates into the pattern and the pattern swells. By including a highly polar repeating unit in the resin, the affinity between the resin and the developer containing the organic solvent is lowered, and the developer containing the organic solvent is less likely to penetrate into the pattern, so that swelling is suppressed. Is considered. However, in the dot pattern that has a smaller area of adhesion to the substrate than the line and space pattern, the effect of swelling due to the penetration of the developer is even greater, and it is usually solved simply by using a resin containing highly polar repeating units. No. The reason why the problem has been solved by the present invention is not clear, but it is estimated that the highly polar repeating unit according to the present invention has a strong interaction with the substrate surface specifically, and the adhesion to the substrate is enhanced. Yes.

[Actinic ray-sensitive or radiation-sensitive resin composition]
Hereinafter, the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention will be described.
The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention has a negative development (when exposed, the solubility in the developer decreases, the exposed area remains as a pattern, Development for removing the exposed portion). The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention is an actinic ray-sensitive or radiation-sensitive material for organic solvent development used in development using a developer containing an organic solvent. It is a resin composition. Here, the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.
The actinic ray-sensitive or radiation-sensitive resin composition is typically a resist composition, and preferably a chemically amplified resist composition.

  The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention includes (A) a repeating unit represented by the following general formula (1) and having a ClogP value of 2.2 or less, It contains a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent.

Additional components that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition used in the present invention include resins other than the resin (A), basic compounds, crosslinking agents, surfactants, organic carboxylic acids, and carboxylic acids. An onium salt is mentioned.
Hereafter, each component mentioned above is demonstrated in order.

[Resin (A)]
In the present invention, the resin (A) contains a repeating unit represented by the following general formula (1) and has a ClogP value of 2.2 or less, and the solubility in a developer containing an organic solvent is reduced by the action of an acid. Resin.

In general formula (1), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, or a carboxyl group, and L represents a single bond or a divalent group. Represents a linking group. R ₂ or R ₃ and L may combine with each other to form a ring, in which case either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Represent. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.

R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom.
The alkyl group for R ₁ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ₁ is preferably a hydrogen atom or a methyl group.

L represents a single bond or a divalent linking group. As the divalent linking group represented by L, a monocyclic or polycyclic aromatic ring optionally having a substituent having 6 to 18 carbon atoms, —C (═O) —, —O—C (= O) —, —CH ₂ —O—C (═O) —, a thiocarbonyl group, a linear or branched alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6), linear Alternatively, a branched alkenylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6), a cycloalkylene group (preferably having 3 to 10 carbon atoms, more preferably 3 to 6), a sulfonyl group, -O-, -NH-, -S-, a cyclic lactone structure or a divalent linking group in combination thereof (preferably having a total carbon number of 1-50, more preferably a total carbon number of 1-30, and even more preferably a total carbon number of 1-20 ).
L represents a single bond, -COO -, - CONH -, - O -, - OCO -, - NHCO -, - COOCH 2 -, - COOCH 2 CH 2 -, - CONHCH 2 -, or -CONHCH ₂ CH ₂ - Is preferably represented.
L may combine with R ₂ or R ₃ to form a ring, and in this case, L represents a trivalent linking group. Examples of the trivalent linking group in this case, the divalent removing 1 comprising group a hydrogen atom from the connecting group. _{Particularly, -CONH-L A - (L} A represents a divalent linking group It is preferably a group formed by removing one hydrogen atom from a divalent linking group represented by the general formula (LA) described later).

R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group or a carboxyl group.
When R ₂ and R ₃ represent an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.
R ₂ or R ₃ and L may be linked to each other to form a ring, in which case R ₂ or R ₃ represents a divalent linking group. In this case, the divalent linking group is preferably a carbonyl group, an alkylene group, —O—, —NH—, or a divalent linking group formed by a combination thereof, such as a carbonyl group, an alkylene group, —CONH—, or A divalent linking group formed by combining these is more preferable, and a carbonyl group is still more preferable.
R ₂ and R ₃ are preferably the case where they are linked to a hydrogen atom or L to form a ring.

  Ar represents an aromatic group. Preferable examples of the aromatic group represented by Ar include an aromatic hydrocarbon ring optionally having a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring. Or an aromatic heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. Can be mentioned. Ar is more preferably a benzene ring or a naphthalene ring, and most preferably a benzene ring.

R ₄ represents a substituent, and at least one is preferably a hydroxyl group.
R ₄ is a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), a group represented by the following general formula (N2), It is preferable to represent a group represented by the following general formula (S1) or a group represented by the following general formula (S2). In the following general formula (S1), a hydroxyl group, a hydroxyalkyl group, a carboxyl group, an alkyl group. It is more preferable to represent the group represented by the following general formula (S2), a hydroxyl group, a hydroxyalkyl group (preferably hydroxymethyl group), a carboxyl group, and the general formula (S1). Or a group represented by the above general formula (S2), more preferably a hydroxyl group, a carboxyl group, or a hydroxymethyl group. Is preferable.

In General Formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
In General Formula (N2), R _N3 represents a substituent, and R _N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

In General Formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent, and preferably represent a hydrogen atom or a methyl group.
In general formula (N2), R _N3 represents a substituent, and preferably represents a methyl group. _RN4 represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom.
In general formula (S1), R _S1 represents a substituent, and preferably represents a methoxy group or an amino group. When R _S1 represents an amino group, the general formula (S1) is represented by the following general formula (S3).

In general formula (S3), R _S2 and R _S3 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S3), R _S2 and R _S3 each independently represent a hydrogen atom or a substituent, and preferably represent a hydrogen atom or a methyl group.
In general formula (S2), R _S4 represents a substituent, and preferably represents a methyl group. R _S5 represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom.

In the general formula (1), an alkyl group as R ₁ , an alkyl group as R ₂ and R ₃ , a divalent linking group as R ₄ and L, and Ar each may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms), an alkynyl group (2 to 12 carbon atoms). Is preferable), a cycloalkyl group (which may be monocyclic or polycyclic and preferably has 3 to 12 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms), a hydroxy group, an alkoxy group, alkyl and aryl. Oxycarbonyl group, carbamoyl group, carbamoyloxy group, alkyl and aryloxycarbonylamino group, acylamino group, alkyl and arylthio group, aminocarbonylamino group, sulfamoyl group, alkyl and arylsulfonylamino group, halogen atom, haloalkyl group and alkyl and An aryloxysulfonyl group is mentioned. Preferable examples include an alkyl group, a cycloalkyl group, a halogen atom, a haloalkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an alkyl and aryloxycarbonyl group, an aryl group, and more preferable examples include an alkyl group, A halogen atom, a hydroxy group, and an alkoxy group are mentioned. Examples of the halogen atom are the same as those described for R ₁ above.
The substituent may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, and an alkoxy group. Examples thereof include a carbonyl group, an aryl group, an alkoxyalkyl group, and a group obtained by combining these, and those having 8 or less carbon atoms are preferable.

  n represents an integer of 0 or more, preferably an integer of 1 to 3.

  The general formula (1) is preferably represented by the following general formula (2).

In general formula (2), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, or a carboxyl group, and L represents a single bond or a divalent group. Represents a linking group. R ₂ or R ₃ and L may combine with each other to form a ring, in which case either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Represent. R ₄ represents a substituent, and n ² represents an integer of 0 to 4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.

In the general formula _{(2), R 1, R} 2, R 3, R 4 and L has the general formula (1) is _{R 1,} R _2, R 3, same meanings as _{R 4} and L, specific examples and The preferable range is also the same.

In General Formula (2), n ² represents an integer of 0 to 4, preferably represents an integer of 0 to 2, and more preferably represents 1 or 2.

  The repeating unit represented by the general formula (1) is more preferably represented by the following general formula (3) or (4).

In General Formula (3), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, and L represents a single bond or a divalent linking group. R ₄ represents a substituent. n ² represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.

In general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.

In the general formula _(3), R 1, _{R 4} and L has the general formula (1) have the same meanings as _R 1, _{R 4} and L are the same also specific examples and preferred ranges.

The general formula (3) in, ^{n 2} the general formula (2) they have the same meaning as ^{n 2,} preferably 0 to 2, more preferably 1 or 2.

In the general formula (4), R ₄ has the same meaning as R ₄ in the general formula (1), the same applies to specific examples and preferred ranges.

In the general formula (4), ^{n 3} represents an integer of 0 to 4, preferably 0-2.

  In General Formula (4), A represents a single bond or a divalent linking group, and A is preferably a single bond or a divalent linking group represented by the following General Formula (LA).

In General Formula (LA), A ₁ represents an alkylene group or an arylene group, and A ₂ represents O, S, C═O, C (═O) —O, O—C (═O), NR, C (= O) —NR, NR—C (═O) (R represents a hydrogen atom or an alkyl group), or a single bond, and na represents an integer of 1 or more. If A ₁ and A ₂ there are a plurality, the plurality of A ₁ and A ₂ may be the same or different. * Represents a bond bonded to the nitrogen atom of maleimide.

A ₁ is preferably an alkylene group, A ₂ is preferably O, C (═O) —O, O—C (═O), or a single bond, and na is an integer of 1 to 4. It is preferable.

  The general formula (4) is preferably represented by the following general formula (4a).

In general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ² represents an integer of 0 to 4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.

In General Formula (4a), R ₄ has the same meaning as R ₄ in General Formula (1), and specific examples and preferred ranges thereof are also the same.

In the general formula (4a), ^{n 3} have the same meanings as defined in formula (4) ^{n 3} in, preferably 0-2.

  In General Formula (4a), p represents an integer of 0 to 4, and preferably represents an integer of 0 to 2.

  The resin (A) needs to have a ClogP value of 2.2 or less and 2.0 or less from the viewpoint of reducing the affinity with a developer containing an organic solvent and suppressing penetration into the pattern. It is preferable that it is 1.8 or less. In order to improve the solubility of the developer in the unexposed area and improve the resolution, the ClogP value is preferably −0.2 or more, more preferably −0.06 or more.

  In general, the logP value can be obtained by actual measurement using n-octanol and water, but in the present invention, a distribution coefficient (ClogP value) calculated from a logP value estimation program is used. Specifically, “ClogP value” in the present specification refers to a ClogP value obtained from “ChemBioDraw ultra ver.12”.

  The ClogP value of the repeating unit in the present specification is a value calculated by the above method for a compound in which both ends of the repeating unit are methyl groups.

  The content of the repeating unit represented by the general formula (1), (2), (3), (4) or (4a) is a resin (A 2) to 70% by mole, more preferably 5 to 50% by mole, and particularly preferably 5 to 30% by mole based on all repeating units contained in

  The repeating unit represented by the general formula (1), (2), (3), (4) or (4a) contained in the resin (A) may be one type or two or more types. .

  The resin (A) is preferably nonionic from the viewpoint of ensuring sufficient developer solubility in the unexposed area.

  Specific examples of the repeating unit represented by the general formula (1), (2), (3), (4) or (4a) include the following structures. In addition, the ClogP value calculated | required by the said method is appended to the example.

  The resin (A) may further contain a repeating unit having a ClogP value larger than 2.2, or may contain a repeating unit having a phenolic hydroxyl group having a ClogP value larger than 2.2.

  The content of the repeating unit having a ClogP value larger than 2.2 or the repeating unit having a phenolic hydroxyl group having a ClogP value larger than 2.2 is 0 to 50 mol% with respect to all repeating units in the resin (A). More preferably, it is 0-45 mol%, More preferably, it is 0-40 mol%.

Resin (A) is a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid.
The resin (A) preferably contains a repeating unit having an acid-decomposable group, and preferably has a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group.
In addition, when it has the repeating unit which decomposes | disassembles by the effect | action of an acid and has a carboxyl group, the solubility with respect to an alkali developing solution will increase by the effect | action of an acid, and the solubility with respect to an organic solvent will decrease.

  The repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group is a repeating unit having a group in which a hydrogen atom of the carboxyl group is substituted with a group that decomposes and leaves by the action of an acid.

As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  As the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group, a repeating unit represented by the following general formula (AI) is preferable.

In general formula (AI):
Xa ₁ represents a hydrogen atom or an alkyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx _{1 to} Rx ₃ are alkyl groups (straight or branched), at least two of Rx _{1 to} Rx ₃ are preferably methyl groups.
Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

The alkyl group represented by Xa ₁ may have a substituent, and examples thereof include a methyl group or a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.

Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
The repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.

  Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxy group. A carbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

The repeating unit represented by formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T is a single bond. Is a repeating unit). More preferably, Rx _{1 to} Rx ₃ are each independently a repeating unit representing a linear or branched alkyl group, and more preferably, Rx _{1 to} Rx ₃ are each independently a repeating unit representing a linear alkyl group. Unit.

Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.

  The content of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group is preferably 20 to 90 mol%, more preferably 25 to 80 mol%, based on all repeating units in the resin (A). More preferably, it is 30-75 mol%.

  Moreover, resin (A) may contain the repeating unit represented by the following general formula (VI).

In general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
As the group Y ₂ leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).

  The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (13).

In general formula (13),
Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
At least two of Q ₃ , M ₃ and R ₃ may be bonded to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group, A phenylene group is preferred.

  Specific examples of the repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

  The resin (A) also preferably contains a repeating unit represented by the following general formula (15).

In general formula (15),
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₄ represents a single bond or a divalent linking group.
Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
At least two of Q ₄ , M ₄ and R ₄₄ may be bonded to form a ring.
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ and R ₄₅ have the same meaning as R _{3 in} the general formula (13), and the preferred range is also the same.
M ₄ has the same meaning as M _{3 in} the general formula (13), and the preferred range is also the same.
Q ₄ has the same meaning as Q _{3 in} the general formula (13), and the preferred range is also the same. Examples of the ring formed by combining at least two of Q ₄ , M ₄ and R ₄₄ include rings formed by combining at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is the same. It is.

As the alkyl group of R _{41 to} R ₄₃ in the general formula (15), a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{41 to} R ₄₃ are preferable.
The cycloalkyl group may be monocyclic or polycyclic. Preferably, a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

Also when R ₄₂ is to form a is L ₄ and ring an alkylene group, the alkylene group, preferably methylene group, ethylene group, propylene group, butylene group, hexylene group, an alkylene having 1 to 8 carbon atoms such as octylene Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable. The ring formed by combining R ₄₂ and L ₄ is particularly preferably a 5- or 6-membered ring.

R ₄₁ and R ₄₃ are more preferably a hydrogen atom, an alkyl group, or a halogen atom, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₂ —OH), A chloromethyl group (—CH ₂ —Cl) and a fluorine atom (—F) are particularly preferred. R ₄₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L ₄ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forms a ring with L ₄ ), and an ethylene group (forms a ring with L ₄ ). .

Examples of the divalent linking group represented by L _4, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
L ₄ is preferably a single bond, a group represented by —COO-L ₁ —, or a divalent aromatic ring group. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group. As the divalent aromatic ring group, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthylene group are preferable, and a 1,4-phenylene group is more preferable.
In the case where L ₄ forms a ring with R _42, examples of the trivalent linking group represented by L _4, from the embodiment described above of the divalent linking group represented by L ₄ 1 single Preferable examples include groups formed by removing any hydrogen atom.

  Specific examples of the repeating unit represented by the general formula (15) are shown below, but the present invention is not limited thereto.

  Moreover, resin (A) may contain the repeating unit represented by the following general formula (BZ).

In general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

  Specific examples of the repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.

  One type of repeating unit having the acid-decomposable group may be used, or two or more types may be used in combination.

  The content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 20 mol% or more and 90 mol% or less with respect to all the repeating units in the resin (A). It is preferably 25 mol% or more and 80 mol% or less, more preferably 25 mol% or more and 75 mol% or less.

The resin (A) preferably further contains a repeating unit having a lactone group.
As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure, and a bicyclo structure in the 5- to 7-membered ring lactone structure, Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. and n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.

  Examples of the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AI). Can do.

In General Formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represent. A linking group represented by a single bond or -Ab ₁ -CO _2- is preferable. Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17).

  The repeating unit having a group having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

  Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto.

  The content of the repeating unit having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the resin (A). .

The resin (A) may further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the permeability of the developer is further lowered, and the swelling of the pattern can be further suppressed. The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group.
Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.

  When the resin (A) has a repeating unit containing an organic group having a polar group, the content thereof is preferably 1 to 30 mol%, more preferably 5 with respect to all repeating units in the resin (A). It is -25 mol%, More preferably, it is 5-20 mol%.

Furthermore, as a repeating unit other than the above, a repeating unit having a group capable of generating an acid (photoacid generating group) upon irradiation with actinic rays or radiation can also be included. In this case, it can be considered that the repeating unit having this photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later.
Examples of such a repeating unit include a repeating unit represented by the following general formula (14).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

  Specific examples of the repeating unit represented by the general formula (14) are shown below, but the present invention is not limited thereto.

  In addition, examples of the repeating unit represented by the general formula (14) include repeating units described in paragraphs [0094] to [0105] of JP-A No. 2014-041327.

  When the resin (A) contains a repeating unit having a photoacid-generating group, the content of the repeating unit having a photoacid-generating group is preferably 1 to 40 mol% with respect to all repeating units in the resin (A). More preferably, it is 5-35 mol%, More preferably, it is 5-30 mol%.

  Resin (A) may contain the repeating unit represented by the following general formula (V-1) or the following general formula (V-2).

Where
R ₆ and R ₇ are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, A halogen atom, an ester group (-OCOR or -COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n ₃ represents an integer of 0 to 6.
n ₄ represents an integer of 0-4.
X ⁴ is a methylene group, an oxygen atom or a sulfur atom.
Although the specific example of the repeating unit represented by general formula (V-1) or (V-2) is shown below, it is not limited to these.

  Resin (A) containing the repeating unit represented by the general formula (1) is, for example, “5th edition Experimental Chemistry Course” page 42, “Macromolecules”, 46, (2013), 8882-8887, or “Bioorganic and Medicinal Chemistry Letters”, 20, (2010) pages 74-77.

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And a solvent that dissolves the actinic ray-sensitive or radiation-sensitive composition in the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.
Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. In a solid state such as reprecipitation method by removing the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent Ordinary methods such as the purification method can be applied.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 30,000, and most preferably 5,000 to 20,000, as a polystyrene-converted value by the GPC method. 000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
Another particularly preferable form of the weight average molecular weight of the resin (A) is 5,000 to 15,000 in terms of polystyrene by GPC method. By setting the weight average molecular weight to 5,000 to 15,000, resist residues (hereinafter also referred to as “scum”) are particularly suppressed, and a better pattern can be formed.
The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and pattern shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive composition in the present invention, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content. .
In the actinic ray-sensitive or radiation-sensitive composition of the present invention, the resin (A) may be used alone or in combination.

[Compound capable of generating acid upon irradiation with actinic ray or radiation (B)]
The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention is a compound that generates an acid upon irradiation with an actinic ray or radiation (“photoacid generator << PAG: Photo Acid Generator” ”or“ Compound (B) ").
The photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A).
In the present invention, the photoacid generator is preferably in the form of a low molecular compound.
The photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred.
The photoacid generator is preferably a sulfonium salt.
More preferable examples of the photoacid generator include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

  Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
The alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), and fluorinated antimony (eg, SbF ₆ ⁻ ). .

  Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

  Moreover, as a non-nucleophilic anion, the anion represented with the following general formula (AN1) is also mentioned as a preferable aspect.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ may be mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

x is preferably 1 to 10, and more preferably 1 to 5.
y is preferably 0 to 4, and more preferably 0.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

  Examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the general formulas (LC1-1) to (LC1-17).

  The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

_Examples of the organic group for R ₂₀₁ , R _202, and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. Preferred examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

In the present invention, the photoacid generator has a volume of 130 to ³ or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. It is preferable that the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 ³ or more (more preferably sulfonic acid). more preferably 270 Å ³ (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 Å ³ or more in size is a compound capable of generating an Particularly preferred. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
In this invention, the photo-acid generator which generate | occur | produces the acid illustrated below by irradiation of actinic light or a radiation is preferable. In addition, the calculated value of the volume is appended to a part of the example (unit ^{３ 3} ). In addition, the calculated value calculated | required here is a volume value of the acid which the proton couple | bonded with the anion part.
One inch is 1 × 10 ⁻¹⁰ m.

  As the photoacid generator, paragraphs [0368] to [0377] of JP2014-41328A, paragraphs [0240] to [0262] of JP2013-228881A (corresponding US Patent Application Publication No. 2015/004533). [0339]) of the specification can be incorporated, the contents of which are incorporated herein. Moreover, although the following compounds are mentioned as a preferable specific example, it is not limited to these.

A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition. More preferably, it is 8-40 mass%. In particular, in order to achieve both high sensitivity and high resolution at the time of electron beam or extreme ultraviolet exposure, the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 10% by mass. 35% by mass.

[Solvent (C)]
The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention contains a solvent (C). This solvent comprises (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one of at least one selected from the group is included. In addition, this solvent may further contain components other than component (M1) and (M2).

  As the component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

As the component (M2), the following are preferable.
As propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferable.
As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred.
Also preferred is butyl butyrate.
As alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferable.
As the alkylene carbonate, propylene carbonate is preferable.

  As the component (M2), propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone or propylene carbonate is more preferable.

  In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.

  Preferred examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and it is particularly preferable to use isoamyl acetate.

  As the component (M2), one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used. Examples of such component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) ) Is preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. Here, “flash point” means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.

  It is preferable that the solvent contains the component (M1). It is more preferable that the solvent consists essentially of the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent contains both the component (M1) and the component (M2).

  The mass ratio of the component (M1) and the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, it is preferable that a solvent consists only of a component (M1) or contains both a component (M1) and a component (M2), and those mass ratios are as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. Employing such a configuration makes it possible to further reduce the number of development defects.

  In addition, when a solvent contains both a component (M1) and a component (M2), mass ratio of the component (M1) with respect to a component (M2) shall be 99/1 or less, for example.

  As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of components other than the components (M1) and (M2) is preferably in the range of 5% by mass to 30% by mass with respect to the total amount of the solvent.

  The content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined so that the solid content concentration of all components is 0.5 to 30% by mass, and is preferably 1 to 20% by mass. More preferably, it is determined. If it carries out like this, the applicability | paintability of actinic-light sensitive or radiation sensitive composition can further be improved.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably carbon). Represents an aryl group (preferably having a carbon number of 6 to 20), in which R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom.
The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.
Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  The amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform. Alternatively, after reacting by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.

(A compound having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from a proton acceptor property to an acidic property (PA) )
The actinic ray-sensitive or radiation-sensitive composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation to decrease the proton acceptor property. It may further contain a compound that generates a compound that has disappeared or changed from proton acceptor properties to acidic properties (hereinafter also referred to as compound (PA)).

  The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

  Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.

  These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of actinic-ray-sensitive or radiation-sensitive composition, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

  As the basic compound, for example, compounds described in paragraphs 0140 to 0144 of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

<Hydrophobic resin>
The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention may have a hydrophobic resin different from the resin (A) separately from the resin (A).
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the membrane, but unlike surfactants, it is not always necessary to have hydrophilic groups in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to
Examples of the effects of adding the hydrophobic resin include control of a static / dynamic contact angle of the film surface with respect to water, suppression of outgassing, and the like.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types. The hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.

  When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.

When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

Further, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in the side chain portion.
Here, the CH ₃ partial structure contained in the side chain portion of the hydrophobic resin, is intended to encompass CH ₃ partial structure an ethyl group, and a propyl group having.
On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (for example, α-methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH ₃ partial structure in the present invention.

  Regarding the hydrophobic resin, the description of [0348] to [0415] of JP-A-2014-010245 can be referred to, and the contents thereof are incorporated in the present specification.

  In addition, as the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a surfactant. By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); EFtop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to known surfactants as described above, the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

  One of these surfactants may be used alone, or two or more thereof may be used in combination.

  When the actinic ray-sensitive or radiation-sensitive composition used in the present invention contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably based on the total solid content of the composition. Is 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%.

<Other additives>
The actinic ray-sensitive or radiation-sensitive composition used in the present invention is a compound that promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer (for example, It may further contain a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group.

  The actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a dissolution inhibiting compound. Here, the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and decreases the solubility in a developer.

The developer of the present invention can also be suitably applied to a non-chemical amplification resist composition.
As a non-chemical amplification resist composition, for example,
Resist materials whose solubility changes when the main chain is cleaved by irradiation with g-line, h-line, i-line, KrF, ArF, EB, EUV or the like and the molecular weight is reduced (for example, JP 2013-210411 A [0025] ]-[0029], [0056] and copolymers of α-chloroacrylic acid ester compounds and α-methylstyrene compounds described in US Patent Publications 2015/0008211 [0032]-[0036], [0063] A resist material mainly composed of
Hydrogen silsesquioxane (HSQ) with silanol condensation reaction generated by g-line, h-line, i-line, KrF, ArF, EB or EUV, calixarene substituted with chlorine,
Metal complexes that absorb light such as g-line, h-line, i-line, KrF, ArF, EB or EUV (magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, A complex of tin, antimony, cesium, zirconium, hafnium, etc., including titanium, zirconium and hafnium, which are preferable from the viewpoint of pattern formation), and ligand exchange process in combination with ligand elimination and acid generator (Japanese Patent Application Laid-Open No. 2015-075500 [0017] to [0033], [0037] to [0047], Japanese Patent Application Laid-Open No. 2012-185485 [0017] to [0032], [0043] to [0044], US Pat. 2012/0208125 [0042] to [0051], [0066], etc.).
Moreover, as a resist composition, the resist composition as described in [0010]-[0062], [0129]-[0165] of Unexamined-Japanese-Patent No. 2008-83384 can also be used.

  Hereinafter, each process which the pattern formation method of this invention has is demonstrated.

<Step (1)>
Step (1) is a step of forming a film using the actinic ray-sensitive or radiation-sensitive composition, and can be performed, for example, by the following method.
In order to form a film on a substrate using an actinic ray-sensitive or radiation-sensitive composition, the resin (A) and the compound (B) are dissolved in a solvent (C) and the actinic ray-sensitive or radiation-sensitive composition is formed. The composition is prepared, filtered as necessary, and then applied onto the substrate. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.

  In the pattern forming method of the present invention, a film (active light sensitive or radiation sensitive film, typically a resist film, chemically amplified) using the actinic ray sensitive or radiation sensitive composition on a substrate. A resist film of a mold is preferable. A topcoat layer may be formed on the actinic ray-sensitive or radiation-sensitive film using a topcoat composition. The thickness of this film is generally 200 nm or less, preferably 10 to 100 nm. The film thickness of the top coat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.

For example, in order to resolve a 1: 1 line and space pattern having a line width of 20 nm or less, the film thickness of the formed film is preferably 50 nm or less. If the film thickness is 50 nm or less, pattern collapse is less likely to occur when a development process described later is applied, and better resolution performance is obtained.
More preferably, the film thickness ranges from 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. More preferably, the film thickness ranges from 15 nm to 40 nm. When the film thickness is within this range, etching resistance and better resolution performance can be satisfied at the same time.

As a method for forming a film, for example, an actinic ray-sensitive or radiation-sensitive composition is used on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit elements, such as a spinner or a coater. The film is formed by applying and drying by an appropriate application method. Various known base films (inorganic films, organic films, antireflection films) can be previously applied to the lower layer of the film.
As a method for applying the actinic ray-sensitive or radiation-sensitive composition on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

In the pattern forming method of the present invention, the top coat composition can be applied to the upper layer of the film by the same means as in the film forming method and dried to form the top coat layer. It is preferable that the top coat is not mixed with a film made of an actinic ray-sensitive or radiation-sensitive composition and can be uniformly applied to the upper layer of the film. Before forming the topcoat layer, it is preferable to dry the film.
Further, the top coat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond. However, a conventionally known top coat can be formed by a conventionally known method. For example, the top coat can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543.
In the development step, for example, a top coat containing a basic compound as described in JP2013-61648A is preferably formed on the film. Specific examples of the basic compound that can be contained in the top coat are the same as those described above.

  As a method for drying the film and the topcoat layer comprising the actinic ray-sensitive or radiation-sensitive composition, a method of drying by heating is generally used. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.

<Step (2)>
Step (2) is a step of exposing the film, and can be performed, for example, by the following method.
The film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.
Although it does not specifically limit as actinic light or radiation, For example, they are KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV, Extreme Ultra Violet), an electron beam (EB, Electron Beam), etc., and extreme ultraviolet rays or an electron beam is especially preferable. . The exposure may be immersion exposure.

<Bake>
In the pattern forming method of the present invention, baking (heating) is preferably performed after exposure and before development. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern shape become better.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

<Step (3)>
Step (3) is a step of developing the film exposed in step (2) with a developer containing an organic solvent.

[Developer]
The developer used in the present invention contains an organic solvent. A developer containing an organic solvent is also referred to as an “organic developer”. The content of the organic solvent in the organic developer is preferably from 50% by mass to 100% by mass, more preferably from 70% by mass to 100% by mass, based on the total amount of the developer. 90 mass% or more and 100 mass% or less is more preferable, and 95 mass% or more and 100 mass% or less is particularly preferable.
The organic solvent contained in the developer is not particularly limited, but at least one selected from the group consisting of ester solvents, ketone solvents, alcohol solvents, ether solvents, amide solvents, and hydrocarbon solvents. The organic solvent is preferable.

  An ester solvent is a solvent having an ester bond in the molecule, a ketone solvent is a solvent having a ketone group in the molecule, and an alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule. The amide solvent is a solvent having an amide bond in the molecule, and the ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In this case, it is applicable to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether is applicable to both alcohol solvents and ether solvents in the above classification.

  Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), and acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol mono Ethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, die Lenglycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4 -Propoxybutyl acetate 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4- Methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate , Propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pen propionate Chill, hexyl propionate, heptyl propionate, butyl butanoate, isobutyl butanoate, pentyl butanoate, hexyl butanoate, isobutyl isobutanoate, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentyl pentanoate, ethyl hexanoate, Propyl hexanoate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, 2-hydroxy Ethyl propionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate It can be mentioned. Among these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, and butyl butanoate are preferably used, and isoamyl acetate is particularly preferable. Preferably used.

  Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, cyclohexanone, and methyl. Examples include cyclohexanone, phenylacetone, methyl ethyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, and γ-butyrolactone. preferable.

Moreover, the ketone solvent may have a branched alkyl group. Examples of the cycloaliphatic ketone solvent having a branched alkyl group include 2-isopropylcyclohexanone, 3-isopropylcyclohexanone, 4-isopropylcyclohexanone, 2-isopropylcycloheptanone, 3-isopropylcycloheptanone, 4-isopropylcyclohexane. Examples include heptanone and 2-isopropylcyclooctanone.
Examples of the acyclic aliphatic ketone solvent having a branched alkyl group include diisohexyl ketone, methyl isopentyl ketone, ethyl isopentyl ketone, propyl isopentyl ketone, diisopentyl ketone, methyl isobutyl ketone, and ethyl isobutyl ketone. , Propylisobutylketone, diisobutylketone, diisopropylketone, ethylisopropylketone, methylisopropylketone and the like, and diisobutylketone is particularly preferred.
Examples of the cycloaliphatic ether solvent having a branched alkyl group include cyclopentyl isopropyl ether, cyclopentyl sec-butyl ether, cyclopentyl tert-butyl ether, cyclohexyl isopropyl ether, cyclohexyl sec-butyl ether, and cyclohexyl tert-butyl ether.
Examples of the acyclic aliphatic ether solvent having a branched alkyl group include diisohexyl ether, methyl isopentyl ether, ethyl isopentyl ether, propyl isopentyl ether, diisopentyl ether, methyl isobutyl ether, ethyl isobutyl ether. Propyl isobutyl ether, diisobutyl ether, diisopropyl ether, ethyl isopropyl ether, methyl isopropyl ether and the like, and diisobutyl ether or diisopentyl ether is particularly preferable.

  Examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl-2 Pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dityl-2-hexal, 6-methyl-2-heptanol, 7 -Alcohol (monohydric alcohol) such as methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol, 3-methoxy-1-butanol, ethylene glycol, diethylene glycol, triethylene glycol, etc. Glycol solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, ethyl Glycol ether solvents such as glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, etc. Can be mentioned. Among these, it is preferable to use a glycol ether solvent.

  Examples of ether solvents include glycol ether solvents containing hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole. Aromatic ether solvents, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like. Preferably, an glycol ether solvent or an aromatic ether solvent such as anisole is used.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane. Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc. And aromatic hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene, and the like.
The unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain. Cis and trans isomers having a double bond may be mixed.

  When the developer contains another solvent, the content of the other solvent is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably based on the total mass of the developer. It is 10 mass% or less, Most preferably, it is 5 mass% or less. By making the content of the other solvent 40% by mass or less, the pattern collapse performance can be further improved.

The developer preferably contains a surfactant. Thereby, the wettability with respect to the film is improved, the developability is improved, and the generation of foreign matters tends to be suppressed.
As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
When a developing solution contains surfactant, it is preferable that content of surfactant is 0.001-5 mass% with respect to the total mass of a developing solution, More preferably, 0.005-2 mass %, And more preferably 0.01 to 0.5% by mass.

  The developer preferably contains an antioxidant. Thereby, generation | occurrence | production of an oxidizing agent with time can be suppressed and content of an oxidizing agent can be reduced more.

As the antioxidant, known ones can be used, but when used for semiconductor applications, amine-based antioxidants and phenol-based antioxidants are preferably used.
Examples of amine-based antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2. -Naphthylamine antioxidants such as naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N ' -Di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenyle Phenylenediamine antioxidants such as diamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p, p'-di- t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyl Diphenylamine oxidation such as diphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine Inhibitor; phenothiazi And phenothiazine antioxidants such as N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester and phenoselenadine.
Examples of phenolic antioxidants include 2,6-di-tert-butylphenol (hereinafter, tertiary butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol. 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4′-methylenebis ( 2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-bis (2-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) 4,4′-isopropylidenebis (2,6-di-t-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6- Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol , 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4- Hydroxy-3,5-di-t-butylphenyl) stearyl propionate, oleyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4 Hydroxy-3,5-di-t-butylphenyl) dodecylpropionate, decyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5- Octyl di-t-butylphenyl) propionate, tetrakis {3- (4-hydroxy-3,5-di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-) t-butylphenyl) propionic acid glycerin monoester, ester of 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid and glycerin monooleyl ether, 3- (4-hydroxy-3,5 -Di-t-butylphenyl) propionic acid butylene glycol diester, 3- (4-hydroxy-3,5-di-t-butylpheny ) Propionic acid thiodiglycol diester, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,6-di-t-butyl-4- (N, N′-dimethyl) Aminomethylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, tris {(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) i Sosocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl} sulfide, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 -Dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4-tert-butyl-3-hydroxybenzylsulfide), 6- (4-hydroxy-3,5-di-tert-butylanilino)- 2,4-bis (octylthio) -1,3,5-triazine, 2,2-thio- {diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl)} propionate, N , N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy- 5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis {3,3'-bis -(4'-hydroxy-3'-t-butylphenyl) butyric acid} glycol ester and the like.

  Although content of antioxidant is not specifically limited, 0.0001-1 mass% is preferable with respect to the total mass of a developing solution, 0.0001-0.1 mass% is more preferable, 0.0001-0 More preferred is 0.01 mass%. When it is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when it is 1% by mass or less, development residue tends to be suppressed.

The developer preferably contains a basic compound. Specific examples of the basic compound include compounds exemplified as basic compounds that can be contained in the actinic ray-sensitive or radiation-sensitive composition described later.
Of the basic compounds that can be contained in the developer, a nitrogen-containing compound can be preferably used.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.
The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
The temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

  As the developer, the developer described above is preferably used.

  As the developer used in the development step, development with an alkali developer (so-called double development) may be performed in addition to the development using the developer described above.

<Rinse process>
The rinsing step is a step of rinsing (rinsing) with a rinsing liquid after the developing step.

In the rinsing step, the developed wafer is cleaned using the rinsing liquid described above.
The method of the cleaning process is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary discharge method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among these, a cleaning process is performed by a rotary discharge method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
The rinse time is not particularly limited, but is preferably 10 seconds to 300 seconds, more preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.
The temperature of the rinse liquid is preferably 0 to 50 ° C, and more preferably 15 to 35 ° C.

In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
Furthermore, after the development process or the rinse process or the process with the supercritical fluid, a heat treatment can be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 to 160 ° C. The heating temperature is preferably 50 to 150 ° C, and most preferably 50 to 110 ° C. The heating time is not particularly limited as long as a good resist pattern can be obtained, but is usually 15 to 300 seconds, and preferably 15 to 180 seconds.

As the rinsing liquid, it is preferable to use a rinsing liquid containing an organic solvent. As the organic solvent, the organic solvent contained in the developer (preferably an ester solvent, a ketone solvent, an alcohol solvent, an ether solvent) is used. , At least one organic solvent selected from the group consisting of amide solvents and hydrocarbon solvents).
The organic solvent contained in the rinse liquid is preferably a hydrocarbon solvent.

As the organic solvent contained in the rinsing liquid, when using EUV light (Extreme Ultra Violet) or EB (Electron Beam) in the exposure step, it is preferable to use a hydrocarbon solvent among the above organic solvents, and aliphatic hydrocarbons. It is more preferable to use a system solvent. As the aliphatic hydrocarbon solvent used in the rinsing liquid, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
In addition, although the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
Among the aliphatic hydrocarbon solvents, decane, undecane, isodecane, and dodecane are particularly preferable, and undecane is more preferable.
An unsaturated hydrocarbon solvent can also be used as the hydrocarbon solvent contained in the rinse liquid, and examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like. The number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain. Moreover, when an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.
By using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinsing liquid in this manner, the developer slightly soaked into the film after development is washed away, and swelling is further suppressed. The effect that the pattern collapse is suppressed is further exhibited.

Moreover, you may use the mixed solvent of the said ester solvent and the said hydrocarbon solvent, or the mixed solvent of the said ketone solvent and the said hydrocarbon solvent as an organic solvent contained in a rinse liquid. In the case of the mixed solvent as described above, it is preferable to use a hydrocarbon solvent as a main component.
When an ester solvent and a hydrocarbon solvent are used in combination, it is preferable to use butyl acetate or isoamyl acetate as the ester solvent. Further, as the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint that the above effect is further exhibited.
When a ketone solvent and a hydrocarbon solvent are used in combination, 2-heptanone is preferably used as the ketone solvent. Further, as the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint that the above effect is further exhibited.
In addition, when an ester solvent and a hydrocarbon solvent are used in combination, or when a ketone solvent and a hydrocarbon solvent are used in combination, an unsaturated hydrocarbon solvent can be used as the hydrocarbon solvent. Examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like. The number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain.
Moreover, when an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.

Furthermore, the organic solvent contained in the rinse liquid is an embodiment in which at least one selected from the group consisting of the ester solvent and the ketone solvent is used from the viewpoint of being particularly effective for reducing residues after development. May be.
When the rinse liquid contains at least one selected from the group consisting of ester solvents and ketone solvents, butyl acetate, isopentyl acetate (isoamyl acetate), n-pentyl acetate, ethyl 3-ethoxypropionate (EEP, Ethyl-3-ethoxypropionate) and at least one solvent selected from the group consisting of 2-heptanone as a main component, preferably at least selected from the group consisting of butyl acetate and 2-heptanone It is particularly preferable to contain one solvent as a main component.
When the rinsing liquid contains at least one selected from the group consisting of ester solvents and ketone solvents, the rinse liquid is selected from the group consisting of ester solvents, glycol ether solvents, ketone solvents, alcohol solvents. It is preferable to contain propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl acetate, ethyl lactate, methyl 3-methoxypropionate, cyclohexanone, methyl ethyl ketone, γ- A solvent selected from the group consisting of butyrolactone, propanol, 3-methoxy-1-butanol, N-methylpyrrolidone and propylene carbonate is preferred.
Among these, when an ester solvent is used as the organic solvent, it is preferable to use two or more ester solvents from the viewpoint that the above effect is further exhibited. As a specific example in this case, an ester solvent (preferably butyl acetate) is used as a main component, and an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) having a different chemical structure is used as a subcomponent. Can be mentioned.
When an ester solvent is used as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (one type or two or more types) from the viewpoint that the above effect is further exhibited. Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent.
When a ketone solvent is used as the organic solvent, an ester solvent and / or a glycol ether solvent is used in addition to the ketone solvent (one or two or more) from the viewpoint that the above effects are further exhibited. May be. Specific examples in this case include a ketone solvent (preferably 2-heptanone) as a main component, an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) and / or a glycol ether solvent (preferably propylene). Glycol monomethyl ether (PGME)) is used as an accessory component.
Here, said "main component" means that content with respect to the total mass of an organic solvent is 50-100 mass%, Preferably it is 70-100 mass%, More preferably, it is 80-100 mass%, More preferably, it means 90 to 100% by mass, particularly preferably 95 to 100% by mass.
Moreover, when it contains a subcomponent, it is preferable that content of a subcomponent is 0.1-20 mass% with respect to the total mass (100 mass%) of a main component, 0.5-10 More preferably, it is 1 mass%, and it is further more preferable that it is 1-5 mass%.

  The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. When the rinse liquid is a mixed solvent of a plurality of solvents, it is preferable that the vapor pressure as a whole is in the above range. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

The rinse liquid may contain a surfactant. When the rinsing liquid contains a surfactant, wettability to the film is improved, rinsing properties are improved, and generation of foreign matters tends to be suppressed.
As the surfactant, the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
When the rinse liquid contains a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass with respect to the total mass of the rinse liquid. More preferably, it is 0.01-0.5 mass%.

  The rinse liquid may contain an antioxidant. The antioxidant that the rinsing solution may contain is the same as the antioxidant that the developing solution may contain.

  When the rinse liquid contains an antioxidant, the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, 0.0001 to 0.1% with respect to the total mass of the rinse liquid. % By mass is more preferable, and 0.0001 to 0.01% by mass is even more preferable.

The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention, and various materials (for example, a solvent, a developer, a rinse solution, an antireflection film-forming composition, a topcoat-forming composition, etc. ) Preferably does not contain impurities such as metals, metal salts containing halogen, acids and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
Examples of the method for removing impurities such as metals from various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material obtained by combining these materials and ion exchange media. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
In addition, as a method of reducing impurities such as metals contained in various materials, an apparatus that selects a raw material having a low metal content as a raw material constituting each material, and performs filter filtration on the raw material constituting each material. Examples thereof include a method of performing distillation under a condition in which the inside is lined with Teflon (registered trademark) and contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Container>
As an organic solvent (also referred to as “organic processing solution”) that can be used for the developer and the rinsing solution, it is stored in a container for storing an organic processing solution for patterning a chemically amplified or non-chemically amplified film having a storing portion. It is preferable to use those prepared. As this container, for example, the inner wall of the container contacting the organic treatment liquid is a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention / metal elution prevention treatment is performed. It is preferably a container for containing an organic processing solution for patterning a film, which is formed from an applied metal. An organic solvent that is to be used as an organic processing liquid for film patterning is stored in the storage part of the storage container, and the one discharged from the storage part at the time of film patterning can be used.

  In the case where the storage container further includes a seal portion for sealing the storage portion, the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more resins, or a metal that has been subjected to a rust prevention / metal elution prevention treatment.

  Here, a seal part means the member which can interrupt | block an accommodating part and external air, and can mention a packing, an O-ring, etc. suitably.

  The resin different from one or more kinds of resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

  Examples of perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), and tetrafluoride. Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.

  Particularly preferred perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

  Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.

  As the rust prevention / metal elution prevention treatment, it is preferable to apply a film technology.

  There are three types of coating technology: metal coating (various plating), inorganic coating (various chemical conversion treatment, glass, concrete, ceramics, etc.) and organic coating (rust prevention oil, paint, rubber, plastics). .

  Preferable film technology includes surface treatment with a rust preventive oil, a rust preventive agent, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.

  Among them, various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin esters of higher fatty acids) And chelating compounds such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethyl orange amine trisuccinic acid, diethylene triamine pentic acid, and fluororesin lining. Particularly preferred are phosphating and fluororesin lining.

  In addition, compared with direct coating treatment, it does not directly prevent rust, but as a treatment method that leads to the extension of the rust prevention period by coating treatment, "pretreatment" is a stage before rust prevention treatment. It is also preferable to adopt.

  As a specific example of such pretreatment, a treatment for removing various corrosion factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.

  Specific examples of the storage container include the following.

・ FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining)
・ JFE steel drums (wetted inner surface; zinc phosphate coating)

  Examples of the storage container that can be used in the present invention include the containers described in JP-A No. 11-021393 [0013] to [0030] and JP-A No. 10-45961 [0012] to [0024]. be able to.

  The organic processing liquid of the present invention can be added with a conductive compound in order to prevent failure of chemical pipes and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. good. Although it does not restrict | limit especially as an electroconductive compound, For example, methanol is mentioned. The good addition is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics. Regarding chemical solution piping members, SUS (stainless steel) or various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluorine resin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

In general, the developer and the rinsing liquid are stored in a waste liquid tank through a pipe after use. At that time, when using a hydrocarbon solvent as the rinsing liquid, the solvent in which the resist dissolves again in order to prevent the resist dissolved in the developer from precipitating and adhering to the wafer back surface or piping side surface. There is a way to pass through the pipe. As a method of passing through the piping, after cleaning with a rinsing liquid, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing is mentioned.
The solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl. Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, or the like can be used. Among these, PGMEA, PGME, and cyclohexanone can be preferably used.

  A semiconductor microcircuit, an imprint mold structure, a photomask, and the like can be manufactured by appropriately performing etching treatment and ion implantation using the pattern obtained by the pattern forming method of the present invention as a mask.

  The pattern formed by the above method can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823). The pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, Japanese Patent Application Laid-Open Nos. 3-270227 and 2013-164509.

  In addition, about the process in the case of producing the mold for imprinting using the composition of this invention, patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation of nanoimprint, technical development, and application development, for example" -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".

  The photomask manufactured using the pattern forming method of the present invention is a light reflective mask used in reflective lithography using EUV light as a light source, even if it is a light transmissive mask used in an ArF excimer laser or the like. May be.

  The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.

  An electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) / media-related device, optical device, communication device, etc.). is there.

<Resist composition>
The present invention also relates to a resist composition containing a resin having a repeating unit represented by the general formula (4) or (4a). Specific examples and preferred ranges of the repeating unit represented by formula (4) or (4a) and the resin having this repeating unit in the resist composition of the present invention are as described above.
The resist composition is a preferred embodiment of the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and each component and its content described in the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and others This matter can also be referred to in the resist composition.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.
For samples 21E to 32E, 34E to 50E, 7F to 9F, and 11F, which will be described later, “example” is read as “reference example”.

<Synthesis of Resin A-1>
<< Synthesis of Monomer (a1) >>

(Synthesis of Intermediate a1-1)
30 g of 4-aminophenol was dissolved in 250 ml of tetrahydrofuran, and 27 g of maleic anhydride was carefully added to this solution without excessive heat generation, and the mixture was stirred at room temperature for 3 hours. After the reaction, the solvent was distilled off, and the resulting crude crystals were washed with ethyl acetate to obtain 56 g of intermediate (a1-1).
¹ H-NMR (nuclear magnetic resonance) (DMSO (dimethylsulfoxide) -d6: ppm) δ: 13.67 (br), 10.38 (s), 9.35 (s), 7.43 (d), 6.74 (d), 6.48 (d), 6.30 (d)

(Synthesis of monomer (a1))
56 g of the intermediate (a1-1) was suspended in 240 ml of toluene, 3.7 g of paratoluenesulfonic acid and 28 ml of N, N-dimethylformamide were added, equipped with a Dean-Stark tube and heated to reflux for 5 hours. After allowing to cool to room temperature, this reaction solution was added to 3000 ml of water, and the powder was filtered. After purification by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/1), recrystallization was performed with isopropanol to obtain 22 g of monomer (a1).
¹ H-NMR (DMSO-d6: ppm) δ: 9.68 (s), 7.13 (s), 7.08 (d), 6.83 (d)

<< Synthesis of Resin A-1 >>
5.1 g of monomer (a1), 2.0 g of monomer (c1), 7.7 g of t-butyl methacrylate, 0.48 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Was dissolved in 54.5 g of cyclohexanone. 29.3 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature. The reaction solution was added dropwise to 990 g of a mixed solution of n-heptane and ethyl acetate (n-heptane / ethyl acetate = 9/1 (mass ratio)) to precipitate the polymer, followed by filtration. 300 g of a mixed solution of n-heptane and ethyl acetate (n-heptane / ethyl acetate = 9/1 (mass ratio)) was used to wash the filtered solid. The obtained polymer was dissolved in 82 g of cyclohexanone and dropped into 960 g of a mixed solution of methanol and water (methanol / water = 4/6 (mass ratio)) to precipitate the polymer, followed by filtration. The filtered solid was washed with 290 g of a mixed solution of methanol and water (methanol / water = 4/6 (mass ratio)). Thereafter, the washed solid was subjected to vacuum drying to obtain 12.3 g of resin (A-1). The weight average molecular weight by GPC was 12900, and the molecular weight dispersity (Mw / Mn) was 1.70.
¹ H-NMR (DMSO-d6: ppm) δ: 9.80, 7.15-6.71, 4.76-4.26, 2.93-0.79 (both peaks are broad)

A resin having the following structure was synthesized in the same manner as in the synthesis example of the resin A-1, except that the monomer used was changed. The composition ratio (molar ratio) of the resin was calculated by ¹ H-NMR or ¹³ C-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) and dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement. Table 1 below shows the composition ratio (molar ratio) of repeating units, the weight average molecular weight, the degree of dispersion, and the ClogP value of repeating units for each resin. Moreover, the ClogP value described in Table 1 below is the ClogP value of the repeating unit described at the leftmost among the repeating units contained in each resin.

<Acid generator (B)>
As the acid generator, the following were used.

<Basic compound>
The following were used as basic compounds.

<Solvent (C)>
The following were used as the solvent.
C1: Propylene glycol monomethyl ether acetate C2: Propylene glycol monomethyl ether C3: Ethyl lactate C4: Cyclohexanone

<Developer>
As the developer, the following was used.
SG-1: Anisole SG-2: Methyl amyl ketone SG-3: Isoamyl acetate

<Rinse solution>
As the rinse liquid, the following was used.
R-1: Undecane R-2: Isodecane R-3: Decane R-4: 4-Methyl-2-pentanol

<Crosslinking agent>
The following were used as the crosslinking agent.

<Resist composition>
Each component shown in the following Tables 2 to 4 was dissolved in the solvents shown in Tables 2 to 4. This was filtered using a polyethylene filter having a pore size of 0.03 μm to obtain a resist composition.

<EUV exposure evaluation line and space pattern>
Using the resist composition, a resist pattern was formed by the following operation.

[Application of resist composition and baking after application (PB)]
A resist composition was applied on a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment, and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
One inch is 25.4 mm.

〔exposure〕
The wafer on which the resist film was formed was subjected to EUV exposure with NA (lens numerical aperture) 0.3 and dipole illumination. Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a 1: 1 line and space pattern having a line width of 50 nm.

[Post-exposure bake (PEB)]
After exposure, the wafer was removed from the EUV exposure apparatus and immediately baked for 60 seconds under the temperature conditions shown in Table 5.

〔developing〕
Thereafter, using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) shown in Table 5 was supplied at a flow rate of 200 mL / min while rotating the wafer at 50 rpm (rpm). Development was performed by spraying for a time.

〔rinse〕
Thereafter, the rinse liquid (23 ° C.) shown in Table 5 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rotations (rpm) to perform a rinsing process.
Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.

Evaluation of resist pattern The obtained resist pattern was evaluated for sensitivity and resolving power by the following methods. The resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The results are shown in Table 5 below.

(sensitivity)
The optimum exposure amount when resolving a 1: 1 line and space pattern with a line width of 50 nm was defined as sensitivity (Eop1). The smaller this value, the better the performance.

(Resolution)
In Eop1, line and space patterns with different half pitch sizes were created by changing the mask. At that time, the minimum half pitch size at which a separated (1: 1) line and space pattern was obtained was defined as the resolving power. The smaller this value, the better the performance.

<EUV exposure evaluation dot pattern>
Using the resist composition, a resist pattern was formed by the following operation.

[Application of resist composition and baking after application (PB)]
A resist composition was applied on a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment, and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
One inch is 25.4 mm.

〔exposure〕
The wafer on which the resist film was formed was subjected to EUV exposure with NA (lens numerical aperture) 0.3 and dipole illumination. Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming dots with a diameter of 30 nm at a pitch of 100 nm.

[Post-exposure bake (PEB)]
After the exposure, the wafer was taken out from the EUV exposure apparatus and immediately baked for 60 seconds under the temperature conditions shown in Table 6.

〔developing〕
Thereafter, using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) shown in Table 6 was supplied at a flow rate of 200 mL / min while rotating the wafer at 50 rpm (rpm). Development was performed by spraying for a time.

〔rinse〕
Thereafter, the rinse liquid (23 ° C.) described in Table 6 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment.
Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.

Evaluation of resist pattern The resolution of the obtained resist pattern was evaluated by the following method. The resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The results are shown in Table 6 below.

(sensitivity)
The optimum exposure amount when resolving a dot with a diameter of 30 nm was defined as sensitivity (Eop2).

(Resolution)
In the above Eop2, by changing the mask, the dot diameter is reduced from 30 nm while maintaining the pitch (interval between dots) at 100 nm, and the limit minimum diameter of the separated dot pattern is defined as the resolution. did. The smaller this value, the better the performance.

<EB exposure evaluation line and space pattern>
Using the resist composition, a resist pattern was formed by the following operation.

[Application of resist composition and baking after application (PB)]
An organic film DUV44 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm. A resist composition was applied thereon and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.

〔exposure〕
The wafer on which the resist film was formed was subjected to EB exposure using an electron beam irradiation apparatus (JBX 6000FS / E manufactured by JEOL; acceleration voltage 50 keV). Specifically, a 1: 1 line and space pattern (length direction: 0.12 mm, number of drawn lines: 20) having a line width of 50 nm was exposed with different exposure amounts.

[Post-exposure bake (PEB)]
After the exposure, the wafer was taken out of the electron beam irradiation apparatus and immediately heated on the hot plate at the temperature shown in Table 7 for 60 seconds.

〔developing〕
Using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) shown in Table 7 is sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm). Development was performed by discharging.

〔rinse〕
Thereafter, the rinse liquid (23 ° C.) shown in Table 7 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment.
Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.

  The resist pattern was evaluated by the same method as the “EUV exposure evaluation line and space pattern” described above. The results are shown in Table 7. The resolving power was evaluated by creating line and space patterns having different half pitch sizes by drawing.

<EB exposure evaluation dot pattern>
Using the resist composition, a resist pattern was formed by the following operation.

[Application of resist composition and baking after application (PB)]
An organic film DUV44 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm. A resist composition was applied thereon and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.

〔exposure〕
The wafer on which the resist film was formed was subjected to EB exposure using an electron beam irradiation apparatus (JBX 6000FS / E manufactured by JEOL; acceleration voltage 50 keV). Specifically, EB exposure was performed while changing the exposure amount so that dots with a diameter of 30 nm were formed at a pitch of 100 nm.

[Post-exposure bake (PEB)]
After the exposure, the wafer was taken out of the electron beam irradiation apparatus and immediately heated on the hot plate at the temperature shown in Table 8 for 60 seconds.

〔developing〕
Using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.), the developer (23 ° C.) shown in Table 8 is sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm). Development was performed by discharging.

〔rinse〕
Thereafter, the rinse liquid (23 ° C.) shown in Table 8 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment.
Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.

  The resist pattern was evaluated by the same method as the “EUV exposure evaluation dot pattern” described above. The results are shown in Table 8. The resolving power was evaluated by drawing so that the dot diameter was decreased from 30 nm.

  As shown in Tables 5 to 8 above, the pattern formed by the pattern forming method of the present invention was excellent in sensitivity and resolution.

Claims (10)

(A) a resin represented by the following general formula ( 4 ), which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is reduced by the action of an acid; and (B) activity A step (1) of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with light or radiation, and (C) a solvent;
A step (2) of exposing the film using actinic rays or radiation, and a step of developing the film exposed in the step (2) using a developer containing an organic solvent to form a negative pattern ( 3) have a,
The pattern formation method whose content of the said organic solvent in the said developing solution is more than 50 mass% and 100 mass% or less with respect to the whole quantity of the said developing solution .

In general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0-4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same.   The pattern formation method according to claim 1, wherein the resin (A) includes a repeating unit having an acid-decomposable group. Formula (4) is represented by the following general formula (4a), a pattern forming method according to claim 1 or 2.

In general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. If R ₄ there are a plurality, the plurality of R ₄ may be different and the same. R ₄ is represented by a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), or a following general formula (N2). The pattern formation method of any one of Claims 1-3 showing group, group represented by the following general formula (S1), or group represented by the following general formula (S2).

In General Formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
In General Formula (N2), R _N3 represents a substituent, and R _N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring. Wherein R ₄ is a hydroxyl group, a hydroxymethyl group, a carboxyl group, a group represented by the group represented by the following general formula (S1), or the following general formula (S2), claim 1-4 2. The pattern forming method according to item 1.

In general formula (S1), R _S1 represents a substituent. * Represents a bond bonded to the benzene ring.
In general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring. Wherein ^{n 3} is an integer of 0 to 2, the pattern forming method according to any one of claims 1 to 5. The compound (B) is a sulfonium salt, a pattern forming method according to any one of claims 1-6. The compound (B), the volume of the generated acid is 130 Å ³ or more 2000 Å ³ or less, the pattern forming method according to claim 7. The resin (A) further comprises a repeating unit having a lactone group, the pattern forming method according to any one of claims 1-8. Method of manufacturing an electronic device including a pattern forming method according to any one of claims 1-9.